Certain fluorimino or azomethine containing compounds

ABSTRACT

8. A compound of the formula: WHEREIN EACH R is selected from the class consisting of fluorine and fluoroalkyl radicals and wherein R groups taken together can form ring systems, which compound comprises a ring which contains a plurality of hetero atoms therein, said ring containing only a single azomethine group, provided that said compound contains no atoms other than carbon, fluorine, nitrogen, oxygen and sulfur atoms. 10. Perfluoro-5,6-dihydro-2H-1,4-oxazine. 12. 1,1,1,1-TETRAFLUOROPERFLUORO-5,6-DIHYDRO-2H-1,4-thiazine.

United States Patent Mitsch 1 July 4, 1972 [54] CERTAIN FLUORIMINO ORAZOMETHINE CONT AINING Primary Examinerl.eland A. Sebastian COMPOUNDSAttorney-Frank A. Steldt, Donald C. Gipple and Temple Clayton [72]Inventor: Ronald A. Mltsch, Falcon Heights, Minn. [73] Assignee:Minnesota Mining and Manufacturing EXEM PLARY CLAIM Company, Saint P l,Mi 8. A compound of the formula:

[22] Filed: Jan. 9, 1964 H 21 Appl. No.: 336,839 (J:Nll

[52] US. Cl. ..260/243 R, 149/109, 260/241,

260/244 R, 260/290 H, 260/290 HL, 260/3] 3.], wherein each R is selectedfrom the class consisting of fluorine 260/566 R, 260/566 D, 260/583 NHand fluoroalkyl radicals and wherein R groups taken together [51] Int.Cl.......... ......C07d 93/10, C07d 87/00, C07d 29/14 can form g y whichcompound comprises a g 53 Field of Search mo/241,583,243 12,244 R, whichContains a plurality of hetero atoms therein, said ring 0 H 290 HL, 313566 R 566 D containing only a single azomethine group, provided thatsaid compound contains no atoms other than carbon, fluorine. [56]defences Cited nitrogen, oxygen and sulfur atoms.

UNITED STATES PATENTS l0. Perfluoro-5,6-d|hydro-2H-l ,4-oxazme.

12. L1, 1 ,l-tetrafluoroperfluoro-5,6-dihydro-2H-l ,4-thiazine,3,337,605 8/1967 Sausen ..260/465.5 3,5 I 5,603 6/1970 Brown et el[49/109 12 Claims, No Drawings CERTAIN FLUORIMINO OR AZOMETHINECONTAINING COMPOUNDS This invention relates to a proces for theproduction of certain fluorinated compounds and more particularly to aprocess of reductive defluorination to form fluoriminoorammethine-containing compounds.

It is an object of the present invention to provide a process for thepreparation of a broad class of useful chemical intermediates. lt isanother object of the invention to provide a process for the preparationof fluorinated oxidants. It is still another object of the invention toprovide certain novel and useful heterocyclic compounds. Other objectsof the invention will become apparent to those skilled in the art fromreading the following specification.

The process of the invention can be represented as follows:

wherein the R groups are fluoralkyl or fluorine. The R groups can alsocombine to form rings (which rings can have oflier rings bonded or fusedthereto). Ordinarily only two of the R groups in a single compound willform a ring system, but in some cases all three R groups will combine toform a fused ring system.

included in the tenn fluoralkyl are perfluoro acyclic, branched andstraight chain perfluoroalkyl radicals as well as perfluoroalkylradicals containing perfluoro carbocyclic and heterocyclic ringsincluding those containing oxygen, sulfur and nitrogen (e.g.perfluoropyridyl, perfluorocyclohexyl, pertluorofuranyl andperfluorocyclohexylethyl) etc. Likewise such perfluoro groups can besubstituted by electro-negative groups which may replace one or morefluorine atoms. Such electronegative groups are characterized by havingHammett meta sigma parameters equal to or greater than 0.3 (H. H. Jaffe,Chem. Reviews, Vol. 53, pp 191-26] (1953)). Such groups includeoxidizing groups such as -NF,, =NF, Cl, Br and the like groups. The Rgroups of the starting compounds of the reaction can also containgroupings of the type in which case the products thereof contain aplurality of groups. Fluoroalkyl radicals thus substituted are includedwithin the scope of R as above defined. Preferably, each R contains notmore than [8 carbon atoms and if the Rs combine to fonn a ring system,they preferably contain not more than 18 carbon atoms between them.Furfller, rings formed of the two R groups on the carbon atoms (whichconsequently include the carbon atom) most preferably certain from threeto seven atoms and those formed by one R group on the carbon atom andthe R group on the nitrogen atom (which consequently include both thecarbon atom and the nitrogen atom) most preferably contain from five toseven atoms. In both of these cases, however, such rings can carryadditional substituents bonded or fused thereto.

The process of the invention is carried out in the presence of areducing agent which is conveniently mixed with a solvent in which ithas at least moderate solubility and which is inert with respect to thereactants and the products of the reaction at the temperature employed.The fluorinated starting material is then brought into contact with thissolution and the reaction is spontaneously initiated. The products ofthe reaction are generally liquids under the conditions of the reactionand are recovered by conventional techniques, e.g. by distillation andcondensation in one or more suitably cooled traps and/or by preparativevapor phase chromatographic techniques. The reduction step is generallyaccompanied by mild exotherm and proceeds smoothly to completion,quantitative or near quantitative yields being obtained in many cases.The length oftimerequiredforthereactionvarieswidely,depending upon thefluorocarbon reactant and particular conditions selected.

Moderate strength reducing agents are generally preferredtothestrongerredueingagentssincethereactionismoreeasily controlled whenthey are used. The preferred reducing agents are sandwich bondedorgano-rnetallic reducing agents and derivatives thereof, otherorgano-metallic reducing agents and inorganic reducing agents which havereducing capacities equal to or greater than that of iodide. Among theparticularly useful reducing agents are dicyclopentadienylrnanganese(ll), dicyclopentadienylruthenium (ll), dicyclopentadienylnickel (ll),dicyclopentadienyltitanium (II) and dicyclopentadienyliron (H) as wellas substituted derivatives thereof, dicumenechromiun (I1),dibenzenechromium (ll), potassium iodide, potassium bromide, diphenylamine, hydroquinone, etc.

The solvent which is chosen for any particular reaction according to theinvention will depend upon the reactants and the conditions to be used,that is, upon the ability of the solvent to dimolve at least a moderateamount of the reducing agent and upon its inertness with respect to themateriab present at any stage of the reaction. Ordinarily when potassiumiodide is utilized as the reducing agent, aqueous acetonitrile is thepreferred solvent. When a sandwich-type reducing agent is utilized,solvents such as xylene hexafluoride, benzotrifluoride, acetonitr'ile,benzene, carbon tetrachloride, fluorotrichloromethane,difluorodichloromethane, low polymers (oils) of trifluorochloroethene,tetrahydrofuran, dioxymethane and the like can be utilized.

The process is preferably carried out in the range of from about (II to50 C. Although some reaction occurs in many cases below this temperaturerange, it is unnecessarily slow and there are no compensating advantagesto such lower reaction temperatures. At temperatures above this range,on the other hand, the rate of the reaction is often excessive and thereis a possibility of the degradation of either the fluorinated reactantor the product. Since both the reactants and the products are fluorineoxidizing agents which may react violently and even explosively, theyshould be handled with care.

The fluorinated starting materials can generally be obtained byelectrofluorination of the desired hydrocarbon amines. They areordinarily liquids at ambient temperatures and are handled with suitabletechniques to avoid the use of unnecessarily high pressures. Theyinclude perfluoroethylamine, perfluorododecylamine,perfluoro-di-n-dodecylamine, perfluoro- Z-ethyloctadecylamine,perfluorocyclopentylamine, perfluorocycloheptylamine,perfluoropyrrolidine, perfluoropiperidine, perfluoroazacycloheptane,perfluoro-2- dodecylpyrrolidine, perfluoro-2-octylpiperidine,perfluoro-2- ethylazacycloheptane, etc.

The products of the process of the invention are generally useful asfluorochemical intermediates, (e.g. in the preparation of fluorochemicalacids, fluorochemical secondary amines, polymers, and other types ofmateriah) and as fluorinated oxidants (for example, for bleaching andthe like, for oxidizing agents in chemical synthesis. and, when combinedwith proper fuels and binders, as oxidizers in propellants and thelike). Among the products of the process of the invention includeperfluoromethylimine, perfluoroethylimine, perfluorohyxylirnine,perlluorooctadecylimine, perfluoro-S- azatetradecenei, perfluoro-ll-an-nonaooseneJO, perfluoro-Z-ethylpentylimine,perfluoro-2-nonyldodecylimine, perfluror-Z-azaisopentene-Z, perfluorol3-azal 4-methylpentacosene- 1 3 perfluorol9-aza-20-octadecylheptatriacontenel9, perfluorocyclopentylimine,perfluorocyclohexylimine, pertluorocycloheptylimine,perfluoro-N-methylirninocyclopentane,perfluoro-N-heptyliminocyclohexane,perfluoro-N-dodecyliminocycloheptane, perlluoropyrroline, per

fluoro-A-piperideine, perfluoro-A-azacycloheptane,perfluoro-Z-decylpyrroline, perfluoro-2-octyl-N-piperideine,perfluoro-Z-ethyl-A'-azacycloheptene, etc.

In order to more clearly disclose the process of the invention, a numberof specific examples will now be given. All 5 parts are by weight unlesotherwise designated. For convenience, the reactants and products whichappear in the examples are identified by structure in Table 1.

TABLE I Example R R CFNFR C=NR l5 R R 1 C31 1 0&1

CFNF| CZNF F F 2.. CF; CF:

CFNFC Fr C=NCgFs F F 3 CIl ll CaFn CFNF; C=NF CF: CF:

CF-NFCF: C=NC Fr CF: C

5 CF9CF: CFz-CF:

0&1 /CFNF: Cg /C=NF CF CF, CFr-CF:

6 CF;CF1 CFr-CF;

CF: CF-NFCF; CF: C NOF:

CF CF: CFz-CF:

7 CFr-C F: CFr-CF 4O 0&1 /NF Ci:

CF C F1 CF1CF1 8 NF-C1 /N-C{ CF: /NF CF /N NF-CF: \=CF 9 CFg-CF: CF:-CF

/NF /N CFg-C-CSF" F2C-C| n and CFr-OF;

CFg-CC3Fl1 l0 CFCl; CFC]:

CF-NF C=NF F F 11.. CF NF1 CF=NF CF: CF CFr-NF: CF=NF 12.. CFzCF: /CF:CF

O\ /NF O\ /N CFr C F: C l CFg l3... /C Fz C/{z /CF: C{ 7o (){2 /NF (1&2/N

(BF-CF CFCF CF! CF Ci; /CF

c F=( r cn-c F;

butylamine by the electrochemical process (1. H. Simons, US. Pat. No.2,5l9,983, I950). The crude perfluoro-n-butylamine is collected in dryice cooled traps. After fractional distillation of this crude product aliquid fraction is obtained which is identified as 40 percentperlluorom-butylamine as a solution in perfluorobutane. This material isfurther purified by preparative scale vapor phase chromatography. Thepurified material has a molecular weight of 270 (as compared to acalculated value of 271 and a boiling point of about 30.5 C. Theinfrared absorption spectrum and the nuclear magnetic resonance spectrumindicate that this product is perfluoro-nbutylamine.

A dry 5 cc. capacity heavy-walled glass ampoule is charged with 0.37]grams (1.99 X [0' mole) of dicyclopentadienyliron and 1.5 ml. of carbontetrachloride. This mixture is cooled to liquid nitrogen temperature anddegassed by reducing the pressure in the ampoule to not more than about0.1 mm of mercury pressure. A 0.251 gram (9.25 X l0" moles) sample ofperfluoro-n-butylamine is then introduced into the ampoule bycondensation and the ampoule is sealed. The reactants are then allowedto come to room temperature (i.e. approximately 25 C.). The mixture isallowed to stand for 6 days at 25 C. during which time the ampoule isshaken occasionally. At the end of this time the ampoule is cooled toliquid nitrogen temperature and opened. The reaction mixture issubjected to separation by preparative vapor phase chromatographictechniques with the result that the yield of 82.2 percent of theoreticalof perfluoro-n-butylimine is recovered. This material boils at 22 C. andcontains 20.4 percent of carbon, 72.2 percent of fluorine and 6.0percent of nitrogen as compared to calculated values of 20.6 percent,73.4 percent and 6.0 percent, respectively. The molecular weight of thisproduct is found to be 230 as compared to a calculated value of 233. Theinfrared and nuclear magnetic resonance spectra of this material supportthe assigned structure.

EXAMPLE 2 Preparation of perfluoro-3-azapentene.

Perfluorodiethylamine is prepared utilizing the electrochemical processof US. Pat. No. 2,519,983 (Sirnons, 1950) from diethylamine. Thereaction product of the electrochemical step is fractionaily distilledto yield a mixture of the structural isomers perfluorodimethylethylamineand perfluorodiethylarnine and the ratio of 4.5 to 1.Perfluorodiethylarnine is obtained from this mixture by preparativescale chromatographic separation (94 percent perfluorodiethylamine). Themolecular weight of this material is found to be 269 as compared to acalculated value of 271. Its boiling point is 26 C. The infrared andnuclear magnetic resonance spectra are consistent with the assignedstructure.

0.93 Grams (5.0 X moles) of dicyclopentadienyliron and about 2 cc. of atetramer of trifluorochloroethylene are mixed to form a grease. Theinside walls of a 50 ml. heavywalled glass ampoule (which is fitted witha 24/40 joint and stop cock) are coated with this grease by means of aspatula. The ampoule is then cooled to liquid nitrogen temperature andthe contents thereof degassed by reducing the pressure in the ampoule tonot more than about 0.1 mm of mercury pressure. 0.678 Grams (2.5 X 10'moles) of perfluorodiethylamine are then introduced into the ampoule bycondensation and the ampoule is sealed by closing the stop cock. Thereactants are then allowed to come to room temperature (i.e.approximately 25 C. and are allowed to stand for 2 hours at thattemperature. At the end of this time the ampoule is opened and thedesired product, perfluoro-3azapentene, is separated from the reactionmixture by preparative vapor phase chromatographic trapping techniques.A 84.2 percent conversion to this product is obtained. Its boiling pointis 14 C. as compared to a value of 13 to 13.5 C. reported in U.S. Pat.No. 2,643,267 (W. H. Pearlson and L. .l. l-lals, 1953), its molecularweight is found to be 232 as compared to calculated value of 233. Theinfrared spectrum of this product is identical to that of theperfluoro-3-azapentene obtained by the pyrolysis ofperfluorotriethylamine, the process utilized to obtain it in U.S. Pat.No. 2,643,267. The nuclear magnetic resonance spectra is also consistentwith the assigned structure.

EXAMPLE 3 Preparation of perfluoro-Z-methylhexylimine.

Perfluoro-Z-methylhexylamine is prepared utilizing the electrochemicalprocess of Simons, U.S. Pat. No. 2,519,983 (1950) from2-methylhexylamine. The crude fluorination product is purified byfractional distillation followed by preparative vapor phasechromatography. The molecular weight of the purified product, as well asthe infrared and fluorine nuclear magnetic resonance spectra areconsistent with the assigned structure.

In a dry l0 cc. heavy walled glass ampoule are placed 0.67 grams (3.6 XlO' moles) of dicyclopentadienyliron and about 3 cc. of xylenehexafluoride. This mixture is cooled to -l96 C., degassed and 0.75 grams(1.78 X l0 moles) of pertluoro- 2-methylhexylarnine are then introducedinto the ampoule by condensation. After sealing, the ampoule is allowedto stand at room temperature for l2 days afier which it is cooled toliquid nitrogen temperature and opened. Fractional distillationcondensation of the crude product followed by preparative vapor phasechromatography results in a product of high purity which exhibits theexpected infrared and nuclear magnetic resonance spectra forperfluoro-Z-methylhexylimine.

EXAMPLE 4 Preparation of pert'luoro-Z-azaisopentene-Z.

The reactant perfluoro-N-isopropylmethylamine is prepared by theelectrofluorination of N-isopropylmethylamine using the processdescribed in U.S. Pat. No. 2,5 l9,983 I950). The purified material has aboiling point in the expected range and infrared and nuclear magneticresonance spectra consistent with the structure.

A dry-box is employed for the addition of 0.813 grams (3.0 X 10* moles)of dicumene chromium and 3-4 cc. of xylene hexafluoride to a 10 cc.glass ampoule. After degassing at liquid nitrogen temperature, 0.41grams (L46 X 10'' moles) of perfluoro-N-isopropylmethylamine are thenintroduced to the ampoule by condensation and the ampoule is sealed. Thereaction vessel is allowed to warm to and remain at room temperature fora period of 4 hours during which time the vessel is periodically shaken.At the end of that time the vessel is opened and the desired product,perfluoro-2-azaisopentene-2, is separated from the remainder of thereaction mixture by chromatography. The infrared absorption and nuclearmagnetic resonance spectra supported the assigned structure.

EXAMPLES Preparation of perfluorocyclohexylimine.

Perfluorocyclohexylarnine is obtained by the electroflucrination ofcyclohexylamine. The preparation of this material by theelectrofluorination of aniline has been described in U.S. Pat. No.2,490,099, I949, .l. H. Simons. Afler electrotluorination, the desiredproduct and perfluorocyclohexane prepared in the electrofluorinationreaction are partially separated by fractional distillation and pureperfluorocyclohexylamine is obtained from this material by preparativevapor phase chromatographic trapping techniques. This material is foundto boil at 76'-78 C. (the boiling point reported in the Simon patent is77 C.) and the infrared and nuclear magnetic resonance spectra areconsistent with the assigned structure.

A dry [0 cc. capacity heavy-walled glass-ampoule is charged with 1.49grams (8.0 X 10* moles) of dicyclopentadienyl iron and 5 ml. oftrichlorofluoromethane. This mixture is cooled to liquid nitrogentemperature and degassed by reducing the pressure in the ampoule to notmore than about 0.l mmofmercury pressure. [.33 Grans (4.0 X 10 moles) ofperfluorocyclohexylamine are then introduced into the ampoule bycondensation and the ampoule is sealed. The reactants are allowed tocome to room temperature (i.e. approximately 25 C.). The mixture isallowed to stand for 7 days at 25 C. during which time the ampoule isshaken occasionally. At the end of this time the ampoule is cooled toliquid nitrogen temperature and opened. A crude separation of thedesired product from the remainder of the reaction mixture isaccomplished by fractional distillation-condensation techniques and arelatively pure material is then obtained utilinng chromatography. Thismaterial is found to contain 24.3 percent of car bon, 69.8 percent offluorine and 4.6 percent of nitrogen as compared to calculated values of24.4 percent, 70.8 percent and 4.7 percent, respectively. The infraredabsorption and nuclear magnetic resonance spectra are consistent withthe assigned structure.

EXAMPLE 6 Preparation ofperfluoro-N-methyliminocycloheptane.

The electrochemical process described by Sirnons, U.S. Pat. No.2,519,983 (I950) is employed in the preparation ofperfluoro-N-methylcycloheptylamine from N-methylcycloheptylarnine. Thedesired product is isolated from the reaction mixture by fractionaldistillation under reduced pressure and the purified product is obtainedfrom that distillate by vapor phase chromatography. infrared and nuclearmagnetic resonance spectra are consistent with the asigned structure.

0.664 Grams (4.0 X 10* moles) of potassium iodide dissolved in a 97percent acetonitrile 3 percent water mixture (0.25 X 10 moles ofpotasium iodide per milliter) is placed in a 50cc. glass ampoule andcooled to --l96 C. 0.866 Grams (2.0 X 10" moles) ofperfluoro-N-methylcycloheptylamine is then added as a liquid to thecooled reactor. Afier sealing the reactor, the mixture is allowed towarm to room temperature and react with shaking for a period of 3 hours.Initial separation by fractional distillation-condensation techniques,followed by vapor phase chromatography, is utilized to obtain pureperfluoro-N-methyliminocycloheptane. The identity of the product isconfirmed by infrared and nuclear magnetic resonance spectroscopy.

EXAMPLE 7 Preparation of perl'luro-A-piperideine.

The reactant perfluoropiperidine is prepared by the electrofluon'nationof pyridine as reported by Simmons and Hoffmann in the Journal of theAmerican Chemical Society, 79, 3429, (1957). The purified materialobtained has a boiling point of 48.7-49 C. (compared to a reported valueof 49.5 C.) and has a molecular weight of 283, the same as thetheoretical value. The nuclear magnetic resonance and infrared spectraare consistent with the asigned structure.

sauna.

1.49 Grams (8.0 X 10' moles) of dicyclopentadienyliron and about 1 gramof a tetramer of trifluorochloroethylene are mixed to form a paste. Theinside walls of a 55 ml. capacity heavy-walled glass flask fitted with a24/40 joint and stop cock are coated by applying the paste with aspatula. The flask is cooled to liquid nitrogen temperature and thecontents thereof degased by reducing the pressure in the flask to notmore than about 0.1 mm. of mercury. l.0 Gram (3.54 X 10 moles) ofperfluoropiperidine are then introduced into the ampoule by condensationand the ampoule is sealed. The flask is allowed to come to roomtemperature (approximately 25 C.) and is allowed to stand for 2 hours atapproximately 25 C. At the end of that time the flask is opened and thedesired product, perfluoro-A'-piperideine, is separated from theremainder of the volatile reaction mixture by chromatography. Thepurified product is found to contain 24.1 percent of carbon, 69.0percent of fluorine and 5.5 percent of nitrogen as compared tocalculated values of 24.5 percent, 69.8 percent and 5.7 percent,respectively. This material has a molecular weight of 241 (calculatedvalue 245) and a boiling point of 43 C. (Lit. b.p. 43 C., H. Ulrick, E.Kober, H. Schroeder, R. Ratz and C. Grundmann, J. Org. Chem, 27, 2585(1962)). A conversion of approximately 94 percent is realized (asmeasured by vapor phase chromatography peak areas). The infraredabsorption and nuclear magnetic resonance spectra support the assignedstructure.

EXAMPLE 8 Preparation of cyanuric fluoride.

The direct fluorination of cyanuric fluoride according to the process ofJ. B. Hynes and L. A. Bigelow, J. Am. Chem. Soc. 84, 2751 (1962) isutilized to prepare perfluorohexahydro-striazine. The crude productmixture is concentrated by simple distillation and the pureperfluorohexahydro-s-triazine is obtained by vapor phase chromatography.Infrared, mass and nuclear magnetic resonance spectra confirm theassigned structure of the purified material boiling at 48 C. (Lit. aboveb.p. 1 C

0.223 Grams 1.2 X 10 moles) of dicyclopentadienyliron and 0.5 gram of atetramer of trifluorochloroethylene are mixed to form a paste. Theinside walls of a 10 ml. capacity heavy-walled glass flask fitted with a24/40 joint and stopcock are coated with this paste by means of aspatula. The flask and its contents are cooled to liquid nitrogentemperature and degassed by reducing the pressure in the flask to notmore than about 0.1 mm. of mercury. 0.050 Grams (2.01 X 10" mole) ofperfluorohexahydro-s-triazine are then introduced into the flask bycondensation and the flask is sealed by closing the stopcock. Thereactants are then allowed to come to room temperature (approximately 25C.). After standing for 18 hours at room temperature, the flask iscooled to liquid nitrogen temperature and opened. The volatile productsof the reaction are separated by vapor phase chromatography. Aconversion to cyanuric fluoride of 96.5 percent is realized. Theinfrared spectrum of this material is compared to the spectrum of aknown sample of cyanuric fluoride thus confinning the identity of theproduct.

EXAMPLE 9 Preparation of perfluoro-2-octylpyrroline and perfluoro-5-octylpyrroline.

The electrochemical process described by Sirnons, U.S. Pat. No.2,519,983 (1950) is utilized to prepare perfluoro-2-octylpyrrolidinefrom 2-octylpyrrolidine. A reasonably pure product is isolated from theliquid reaction mixture by vapor phase chromatography using a heatedcolumn. Infrared and nuclear magnetic resonance spectra confirm thestructure as perfluoro-Z-octylpyrrolidine.

0.633 Grams (1.0 X 10' moles) of perfluoro-2-octylpyrrolidine iscondensed into a previously degassed 10 ml. glass ampoule which contains0.585 grams (2.0 X 10' moles) of dicumene chromium and 3 milliliters ofxylene hexafluoride at liquid nitrogen temperature. The reactor issealed and allowed to warm to and remain at room temperature for 4 dayswith periodic shaking. Separation of the reaction mixture isaccomplished by vapor phase chromatography utilizing a column at atemperature greater than C. The infrared and nuclear magnetic resonancespectra are consistent for the C,,F,,N isomers ofperfluorooctylpyrroline.

EXAMPLE 10 Preparation of 2,2-dichlorotrifluorethylimine.

The starting material, 3,3-dichloropentafluoro-L azapropane (b.p. 44 C.)is prepared by the jet fluorination of dichloromalononitrile accordingto the method of L. A. Bigelow (L. A. Bigelow, J. B. Hynes and B. C.Bishop, Second international Symposium on Fluorine Chemistry, EstesPark, Col.,July 17-20, 1962).

The 3,3-dichloropentafluoro-l-azapropane (0.204 g., 1 x 10" moles) iscondensed into a 10 ml. ampoule which contains dicyclopentadienyliron(0.558 g., 3 X 10 moles) and 7 m1. of xylene hepafluoride and is held atliquid nitrogen temperature. Alter the ampoule is sealed, the reactantswarm to and remain at room temperature for a period of 14 days. At theend of this time, the ampoule is opened and its contents are separatedby fractional distillation-condersation techniques utilizing traps at 35and 196 C. The 196 C. fraction is further purified by vapor phasechromatography and yields 34 percent of the theoretical amount of pure2,2- dichlorotrifluoroethylimine. This material is found to contain 14.5percent of carbon and 34.2 percent of fluorine as compared to calculatedvalues of 14.5 percent and 34.3 percent, respectively. The molecularweight of the purified material is 168 as compared to a theoreticalvalue of 166. The infrared and nuclear magnetic resonance spectra areconsistent with the assigned structure.

EXAMPLE I 1 Preparation of perfluoro- 1 ,S-diazal ,4-pentadiene.

The reactant for this example, perfluoro-LS-diazapentane is preparedfrom difluoromalononitrile by the jet fluorination process (L. A.Bigelow, J. B. Hynes and B. C. Bishop, Second lntemational Symposium onFluorine Chemistry, Estes Park, Col., July 17-20, 1962). The purifiedmaterial has a boiling point of 33 C.

A dry 20 cc. glass ampoule is charged with 0.744 g. (4 X 10" moles) ofdicyclopentadienyliron and 10 cc. of xylene hexafluoride. This mixtureis cooled to l96 C. and degassed by reducing the pressure in the ampouleto not more than about 0.1 mm. of mercury pressure. A 0.254 g. (l x 10"moles) sample of perfluoro-l,5-diazapentane is then introduced into theampoule by condensation and the ampoule is sealed. The reactants areallowed to come to room temperature. The mixture is allowed to standwith periodic shaking for 13 days. At the end of this time the contentsare separated by fractionation through 78 and 196 C. traps. The contentsof the -l96 C. receiver are further purified by vapor phasechromatography. The purified product is obtained in a 30.5 percent yieldand identified as perfluoro-l,5-diaza-l,4pentadiene. This materialcontains 19.9 percent of carbon, 62.9 percent of fluorine and has amolecular weight of 181 as compared to calculated values of 20.2percent, 64.0 percent and 178, respectively. The infrared and nuclearmagnetic resonance spectra also support the structure.

EXAMPLE 12 Preparation ofperfluoro-5,6-dihydro-2l-l-1,4-oxazine.

Perfluoromorpholine, the reactant, is prepared by the electrochemicalfluorination of morpholine as described in the literature (T. C. Simmonsand F. W. l-loflmann, J. Am. Chem. Soc., 79, 3429 (1957)). The purifiedmaterial exhibits the expected infrared and nuclear magnetic resonancespectra and a boiling point of 30 C.

To 0.931 grams X l0 moles) of dicyclopentadienyliron is added sufficienttrifluorochlorethylene tetramer oil to result in a paste and this isapplied to the walls of a 50 cc. ampoule by means of a spatula. Theampoule is degassed and cooled to l96 C. and 0.454 g. (1.84 X moles) ofperfluoromorpholine is added by condensation techniques. The mixture isallowed to warm to and remain at room temperature for 45 minutes. Thevolatile reaction mixture is then removed from the ampoule and purifiedby vapor phase chromatography. There is obtained a 42 percent yield ofperfluoro- 5,6-dihydro-2H-l,4-oxazine which exhibits the expectedinfrared and nuclear magnetic resonance spectra. This material has amolecular weight of 213 and contains 22.5 percent carbon and 63.7percent fluorine as compared to calculated values of 21 1, 22.8 percentand 63.0 percent, respectively.

EXAMPLE 13 Preparation of perfluoro-3,4,5,6,7,8,9,lO-octahydroquinolineand perfluoro-2,3,4,5,6,7,8,IO-octahydroquinoline.

Perfluoroquinoline, the starting material for this example, is preparedaccording to Haszeldine (R. N. Haszeldine and F. Smith, J. Chem. Soc.(1956) 783). The pure heterocyclic fluorocarbon. boiling at 130 C., isobtained in low yield by passing quinoline over cobalt trifluoride at400 C. and distillation of the reaction mixture.

Perfluoroquinoline (0.52 grams, l.l7 X 10* moles) is added to a cc.ampoule which contains 0.745 grams (4.0 x lO' moles) ofdicyclopentadienyliron dissolved in 10 cc. of dichlorodifluoromethanecooled to liquid nitrogen temperature. The ampoule is sealed, allowed towarm to room temperature and remain there with periodic shaking over aperiod of 2 weeks. Fractionation of the reaction mixture through 78 andl96 C. receivers separates the product from the solvent. The contentsofthe -78 C. trap are purified by vapor phase chromatography utilizing aheated column of trifluorochloroethylene grease on a diatomaceous earthsupport. The pure product of empirical formula C,F,,N is identified asbeing a mixture of perfluoro-3,4,5,6,7,8,9,l0-octahydroq uinoline andperfluoro-2,3 ,4,5,6,7,8, lO-octahydroq uinoline by infrared and nuclearmagnetic resonance spectroscopy.

EXAMPLE 14 Preparation of l l l l -tetrafluoroperfluoro-5,6-dihydro-2H-l,4-thiazine.

The electrofluorination of tetrahydro-l,4-thian'ne W. Davies, J. Chem.Soc. (1920) I17, 297) to l,l,l,l-tetrafluoro4fluoroperfluorotetrahydro-l,4-thiazine is carried out a generallydescribed by Sirnons (US. Pat. No. 2,519,983, 1950). The pure materialis separated from the fluorocarbon cleavage products by distillation andpreparative vapor phase chromatography. The structure ofl,l,l,l-tetrafluoro-4- fluoroperfluorotetrahydro-l,4-thiazine isconfirmed by infrared and nuclear magnetic resonance spectral analyses.

l ,1, l l -Tetrafluoro-4-fluoroperfluorotetrahydro-l ,4- thiazine (0.341g., l X 10' moles) is condensed into a 20 ml. ampoule cooled to I96containing a magnetic stirring bar, dicyclopentadienyliron (0.372 g., 2X 10'' moies) and 8 ml. of dichloromethane. The ampoule a sealed undervacuum and allowed to warm to and remain at room temperature withstirring for 2 weeks.

After opening the ampoule, the volatile contents are distilled from thesolid residue of ferricinium fluoride. Final purification by vapor phasechromatography on a trifluorochloroethylene grese column at 50 C.affords pure 1 l l l-tetrafluoroperfluoro-5,6-dihydro-2H- l ,4-thiazine.The infrared and nuclear magnetic resonance spectra are consistent withthe proposed structure.

What is claimed is:

l. A process for the preparation of a compound of the formula:

wherein each R is selected from the class consisting of fluorine,perfluorinated groups and perfluorinated groups substituted byelectronegative groups having Hammett meta sigma parameters of at least0.3 and wherein R groups taken together can form rings through the atomsto which they are bonded, which comprises reductively defluorinating acompound of the formula:

wherein the R groups are as previously defined, and isolating thedesired product.

2. A process according to claim 1 wherein two of the R groups arefluorine and the third contains only carbon and fluorine.

3. A process according to claim 1 wherein the desired product containschlorine.

4. A process according to claim 1 wherein at least one of the R groupscontains nitrogen.

5. A process accordingtoclaim wherein the R groups are fluoroalkyl andcontain only carbon and fluorine.

6. A process according to claim I wherein the two R groups on the carbonatom form a ring.

7. A prooem according to claim 1 wherein the R group on the nitrogenatom forms a ring system with one of the other R groups.

8. A compound of the formula:

wherein each R is selected from the clas consisting of fluorine andfluoroalkyl radicals and wherein R groups taken together can fonn ringsystems, which compound comprises a ring which contains a plurality ofhetero atoms therein, said ring containing only a single awmethinegroup, provided that laid compound contains no atoms other than carbon,fluorine, nitrogen, oxygen and sulfur atoms.

9. A compound accrxding to claim 8 which contains only carbon, fluorine,nitrogen and oxygen atoms.

11. A compound according to claim 8 which contains only carbon,fluorine, nitrogen and sulfur atoms.

i 0 i O 0 arms mrv

1. A process for the preparation of a compound of the formula: whereineach R is selected from the class consisting of fluorine, perfluorinatedgroups and perfluorinated groups substituted by electronegative groupshaving Hammett meta sigma parameters of at least + 0.3 and wherein Rgroups taken together can form rings through the atoms to which they arebonded, which comprises reductively defluorinating a compound of theformula: wherein the R groups are as previously defined, and isolatingthe desired product.
 3. A process according to claim 1 wherein thedesired product contains chlorine.
 4. A process according to claim 1wherein at least one of the R groups contains nitrogen.
 5. A processaccording to claim 1 wherein the R groups are fluoroalkyl and containonly carbon and fluorine.
 6. A process according to claim 1 wherein thetwo R groups on the carbon atom form a ring.
 7. A process according toclaim 1 wherein the R group on the nitrogen atom forms a ring systemwith one of the other R groups.
 8. A compound of the formula: whereineach R is selected from the class consisting of fluorine and fluoroalkylradicals and wherein R groups taken together can form ring systems,which compound comprises a ring which contains a plurality of heteroatoms therein, said ring containing only a single azomethine group,provided that said compound contains no atoms other than carboN,fluorine, nitrogen, oxygen and sulfur atoms.
 8. A COMPOUND OF THEFORMULA:
 9. A compound according to claim 8 which contains only carbon,fluorine, nitrogen and oxygen atoms. 10.Perfluoro-5,6-dihydro-2H-1,4-oxazine. 10.PERFLUORO-5,6-DIHYDRO-2H-1,4-OXAZINE. 12.1,1,1,1-TETRAFLUOROPERFLUORO-5,6-DIHYDRO-2H-,1,4THIAZINE.
 11. A compoundaccording to claim 8 which contains only carbon, fluorine, nitrogen andsulfur atoms. 12.1,1,1,1-tetrafluoroperfluoro-5,6-dihydro-2H-1,4-thiazine.